Hard tissue repairing material

ABSTRACT

A hard tissue repairing material includes zirconia as a base material. A surface of the base material has a hydrophilic group. The hydrophilic group is bonded to zirconium atom in the base material. The base material may contain at least an ionic component that is selected from a group consisting of calcium ion, sodium ion, potassium ion, and phosphate ions within the surface. A hard tissue repairing material may include zirconia as a base material and a layer of a main component of an apatite. The layer of the apatite may be formed on a hydrophilic group bonded to zirconium atom in the base material.

TECHNICAL FIELD

The present invention relates to a hard tissue repairing materials and,particularly, to a bone repairing that is used to repair when articularfunction and/or bone function of hands and feet are lost. Furthermore,the invention relates to an implant, that can be used as an artificialtooth root, for rebuilding the teeth and tusks when the teeth had beenlost because of senility or illness.

BACKGROUND ART

Generally, metallic materials, for example, stainless steel and titaniummetal and titanium alloys, ceramic materials, for example,hydroxyapatite (HAP), bioactive-glass, alumina, and zirconia have beenused as biomaterials in practical use. The metallic materials have agood strength and good toughness (tolerance of catastrophic fracture),but have poor corrosion resistance for use in living body. There is adanger of damaging the living tissue because of an elution of metallicmaterials in living body. The hydroxyapatite and the bioactive-glasshave a property of bonding to a living bone (that is to saybioactivity), so that the hydroxyapatite and the bioactive-glass areturned to practical use as bone compensatory materials, a periodontalfilling materials, an artificial vertebra body, and any spacer. Thesematerials have a strength and a toughness that is much less than that ofa living bone, so that these materials have not been used as portionsthat is under high load-bearing conditions, e.g. a femoral bone andtibial bone, and an artificial root of a tooth. As compared with ahydroxyapatite and bioactive-glass, alumina has a high strength and ahigh toughness. However, application of the alumina and the zirconia asa bone repairing material is limited because of non-bioactivity. Aluminahad been turned to a practical use as an artificial root of a tooth, butnow the alumina was replaced by titanium metal and titanium alloysbecause of fragile property peculiar to the ceramics.

As described above, the metallic materials, e.g. titanium metal andtitanium alloys, and the ceramics materials, e.g. alumina and zirconiaare non-bioactive materials that cannot bond to the living bone.Preferably, the bioactive layer that has a good adhesive property tobone are formed, and the bioactive function are given on the surface ofthe non-bioactive materials, in order that the materials are used as abone repairing material and an artificial root of a tooth. Several priorart methods of forming the bioactive layer on the materials have beendisclosed. For example, a method of forming a layer on base materials bya sputtering process or evaporation process is disclosed. The JapaneseLaid-open Patent Publication No. 4-242659 discloses a method of forminga layer on base materials by plasma spraying. The Japanese Laid-openPatent Publication No. 1-203285 discloses a method of forming themixture of zirconia and apatite on the surface of a zirconia cast bycoating and sintering, with the base material limited to zirconia inview of the high strength and high toughness.

By the way, several prior art methods of giving the bioactive functionat the surface of a base materials are disclosed. The Japanese Laid-openPatent Publication No. 6-23030 discloses a method of forming a coatinglayer of silica gel or titania gel on the surface of a base material.The Japanese Laid-open Patent Publication No. 10-179718 discloses amethod of improving the surface of a base material of titanium metal andtitanium alloys to bioactive by soaking in an alkaline fluid.

To form the bioactive layer on the surface of the base materials, thelayer by sputtering, evaporation, and plasma spraying cannot have goodcontact strength to the base materials. Regarding with the layer formedby the Japanese Laid-open Patent Publication No. 1-203285, thebioactivity is declined because of increasing the ratio of zirconia inthe mixture of the zirconia and the apatite, while the adhesive strengthis declined because of increasing the ratio of apatite in the mixture.The layer having the hydroxyl group formed by the method of the JapaneseLaid-open Patent Publication No. 6-23030 are the silica gel layer or thetitania gel layer on the surface of the base materials. Similarly, thebioactive layer formed by the method of the Japanese Laid-open PatentPublication No. 10-179718 are titania phase, titania gel phase,alkaline-titanate phase, and alkaline-titanate gel phase.

DISCLOSURE OF INVENTION

Therefore, it is an object of the present invention to provide a hardtissue repairing material with high mechanically property and highbioactivity.

In accordance with one aspect of the present invention, there isprovided a hard tissue repairing material including zirconia as a basematerial. A surface of the base material has a hydrophilic group, whichis bonded to zirconium atom in the base material.

The base material including the zirconia means that including at leastzirconium dioxide (ZrO₂). The base material may be combined with othermaterials, e.g. alumina. The base material may include a stabilizingagent. The hydrophilic group on the surface of the base material may bea hydroxyl group, a carboxyl group, amino group, carbonate group,sulfonic acid group, and phosphoric group. Specifically, the hydroxylgroup is preferable as functional group capable of inducing the nucleuscreation of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂).

According to the hard tissue repairing material of this invention, ithas a good strength and a good toughness because of the inclusion of thezirconia with good mechanically property. According to the hydrophilicgroup on the surface, an apatite layer may be formed on the surface ofthe base material in the living body, or in the simulated body fluid(hereunder called as “SBF”) with ion concentrations nearly equal tothose of human body fluid. The apatite (hereunder called as “bone-likeapatite”) is the hydroxyapatite which has carbonate ion (CO₃ ²⁻) and lowCa ion concentration (Ca deficiting) regarding with stoichiometriccomposition (Ca₁₀(PO₄)₆(OH)₂). The bone-like apatite also has a Ca/Pratio that is lower than 1.67 of the stoichiometric hydroxyapatite. Thebone-like apatite has a plurality of lattice defect and is constructedby fine particles. Therefore, the bone-like apatite is nearly equal tothe bone apatite of living bone. The bone-like apatite is formed on thesurface of the base material, so that an osteoblast actively grows,differentiates, and forms a collagen and a bone apatite on the bone-likeapatite. That is to say, a new bone tissue is grown from the surroundingliving bone to the surface of the bone-like apatite layer. Then achemical bond between the bone apatite of living bone and the bone-likeapatite is formed, so that the base material may be strongly bonded tothe living bone.

Therefore, in order that the artificial materials can bond to the livingbody, it is necessary that the bone-like apatite may be formed on thesurface of the artificial materials in the living body. The hard tissuerepairing material of this invention has the hydrophilic group, which isbonded to a zirconia in the base material, on the surface without anygel phase so that the hydrophilic group induced a bone-like apatitenucleation on the surface of the base material. Then, the bone-likeapatite is bonded to both the base material and the living bone, so highadhesive strength between the base material and the living bone may begiven.

The zirconia in the base material is preferably a tetragonal zirconiapolycrystals with high strength and high toughness. Preferably, the basematerial includes a stabilizing agent, e.g. ceria and yttria used asstabilizing tetragonal phase. In the presence of the stabilizing agent,the tetragonal zirconia polycrystals can have a high strength and a hightoughness. Specifically, a tetragonal zirconia polycrystals stabilizedwith ceria (Ce-TZP) has a good phase stability without atetragonal-to-monoclinic phase transition, so that the Ce-TZP can keepstably tetragonal phase without a degradation of property in the livingbody and at the hard atmosphere e.g., moisture atmosphere with vapor.Therefore, the base material contains preferably at least an ceria as astabilizing agent. As compared with the tetragonal zirconia polycrystalsstabilized with yttria (Y-TZP), the Ce-TZP has a very high toughness,but has a less strength and a less hardness than those of the Y-TZP.Therefore, in order to compensate for the modest properties, the basematerials containing zirconia is preferably taken into compositematerials with an alumina having high hardness as secondary phase. Inmany composite materials, a zirconia/alumina nano-composite with ceria,which may have nanometer sized alumina particles partly trapped within azirconia crystal particle, indicates much more excellent mechanicalproperties than those of the Y-TZP (see Japanese Patent No. 2703207).Therefore the zirconia/alumina nano-composite is preferably used as thebase material of this invention. Alternatively, the base material maycontain both ceria and yttria as the stabilizing agent.

The zirconia contained in the base material may not be only thetetragonal zirconia polycrystals but also partially stabilized zirconia(PSZ), which has a magnesia or a calcia as a stabilizing agent. Thetetragonal zirconia polycrystals and the partially stabilized zirconiamay contain a small quantity of impurities, such as hafunia and titania.

The hydrophilic group on the surface of the base material is preferablya hydroxyl group (OH group). The Zr—OH group is a functional group thatmay induce an apatite nucleation, so that the bone-like apatite layermay be formed on the surface of the base materials in the living body,or in the SBF. The human body fluid has calcium ions (Ca²⁺) andphosphate ions (PO₄ ³⁻) highly supersaturated with respect to apatite.Therefore, in the living body, the Zr—OH group on the surface takes thecalcium ions, then the Zr—OH group takes the phosphate ions and thecarbonate ions, so a lot of spherical apatite nuclei is formed on thebase materials. The apatite nuclei grows while taking the above ions, sothe bone-like apatite may be formed on the base materials spontaneously.Thus, with the hydroxyl group introduced as the hydrophilic group on thesurface of the base materials containing zirconia, the base materialswith non-bioactivity may be given a bioactivity that is capable to bondto a living bone with chemical bond. This hydroxyl group is bonded to azirconium atom of the zirconia in the base material. The hydroxyl groupmay be formed by modifying the surface of zirconia in the base material.

The base material may contain at least one ionic component selected froma group consisting of calcium ion, sodium ion, potassium ion, andphosphate ions within the surface. With the ionic component containedwithin the surface of the base material, the ionic components of calciumion, sodium ion, potassium ion, and phosphate ions etc are eluted fromthe surface of the base materials in a human body fluid of a livingbody, and in the simulated body fluid. In the meantime, the eluted ioniccomponents in the human body fluid increase the ion concentrations, suchas the hydroxyl ions and calcium ions, etc. Consequently, ionic activityproduct of apatite rises, and may hasten the bone-like apatite layerformation on the base materials in a human body fluid of a living body,or in the simulated body fluid. If the bone-like apatite layer is formedon the surface of the base material soaked in SBF, a bonding period withthe base material and a living bone in a living body may be shortened.It is noted that the thickness of this layer is preferably 1-50micrometer.

A process for producing a hard tissue repairing material includespreparing a base material that has at least a zirconia exposed to thesurface of the base material, and forming a hydrophilic group on thesurface of the base material.

The step of forming the hydrophilic group on the surface of the basematerial may be soaking the base material in an alkaline aqueoussolution or an acid aqueous solution.

The alkaline solution is alkaline, for example, a solution containing asodium hydroxide, a potassium hydroxide, etc. The acid aqueous solutionis acid, for example, a solution containing a hydrochloric acid, anitric acid, a sulfuric acid, and phosphoric acid. Regarding with acondition of soaking the base material in the alkaline aqueous solutionor the acid aqueous solution, a concentration of the alkaline aqueoussolution or the acid aqueous solution is preferably 0.5-20 mol/l, acondition of temperature is preferable 60-140° C.

It is considered that an OH⁻ ion in alkaline solution or a H₃O⁺ ion inacid solution may cut a bond of Zr—O of zirconia in the base material,according to soaking the base material with zirconia on the surface inthe alkaline aqueous solution or the acid aqueous solution. Then a Zr—OHgroup, which is bonded to a zirconium atom, may be formed on the surfaceof the base material. The Zr—OH has a bioactive property. It is a newdiscovery that zirconia, which is not classified as the amphotericoxide, may be improved by both an alkaline aqueous solution and an acidaqueous solution. Furthermore, it is also a new discovery that thehydroxyl group on the surface, which is bonded to a zirconium atom ofthe zirconia in the base material, can induce a nucleus creation ofhydroxyapatite. However, a hydrophilic group formed on an alumina gelthat is classified as amphoteric oxide cannot induce an apatitenucleation by soaking in SBF (Journal of Biomedical Materials Research,1994, Vol. 28, pp 7-15).

It is known that an OH group on a zirconia gel made by the sol-gelprocess may induce a nucleus creation of apatite (Biomeramics volume 11Ed. by R. Z. LeGros and J. P. LeGros, World Scientific, (1998) pp77-80). This zirconia gel is amorphous phase. Even though same Zr—OHgroup, compared the Zr—OH group on the surface of tetragonal zirconiaand monoclinic zirconia of this invention with the Zr—OH on the zirconiagel of amorphous phase, Zr—OH of this invention has high inducement to anucleus creation of apatite. It is considered that the apatite may beeasily grown on rather Zr—OH formed on the surface with crystalstructure than Zr—OH formed on the surface with no crystal structure,because the OH group of the apatite have a coordination to a crystaldirection of the Zr—OH of this invention, when the apatite is created.

In further aspect of the present invention, the process for producing ahard tissue repairing material further includes incorporating an ioniccomponent within the surface of the base material after soaking the basematerial in an alkaline aqueous solution or an acid aqueous solution.

The incorporating the ionic component within the surface of the basematerial is preferably soaking the base material in a molten saltcontaining at least an ionic component selected from the groupconsisting of calcium ion, sodium ion, potassium ion, and phosphateions.

In this process, the hydrophilic group is initially formed on the basematerial, the ionic component is secondly incorporated within the basematerial. Any combination of salts selected from the group consisting ofnitrate, acetate, for example calcium nitrate, sodium nitrate, andpotassium nitrate, and other carbonate, chloride, and phosphate may beused as the molten salt. Preferably, the eutectic mixture in eutecticpoint, at which the melting point is lowest, is used for each saltcombination.

The incorporating the ionic component within the surface of the basematerial is preferably soaking the base material in an aqueous solutioncontaining at least an ionic component selected from the groupconsisting of calcium ion, sodium ion, potassium ion, and phosphateions.

In this process, the ionic component is initially incorporated withinthe base material, secondly, the hydrophilic group is formed on the basematerial. The aqueous solution is a solution containing a metallichydroxide, for example, calcium hydroxide and potassium hydroxide, and asolution of calcium chloride dissolving in dilute hydrochloric acid, anda solution of sodium nitride or potassium nitride dissolving in dilutenitric acid. The concentration of the solution is preferably 0.5-20mol/l, and the temperature of the solution is preferably 60-140° C.

In a yet further aspect of the present invention, the process forproducing a hard tissue repairing material further includesincorporating an ionic component within the surface of the base materialand before forming the hydrophilic group on the surface of the basematerial.

The incorporating the ionic component within the surface of the basematerial is preferably soaking the base material in a molten saltcontaining at least an ionic component selected from the groupconsisting of calcium ion, sodium ion, potassium ion, and phosphateions.

The incorporating the ionic component within the surface of the basematerial is preferably soaking the base material in an aqueous solutioncontaining at least an ionic component selected from the groupconsisting of calcium ion, sodium ion, potassium ion, and phosphateions.

In a yet further aspect of the present invention, the process forproducing a hard tissue repairing material further includes soaking thebase material in the simulated body fluid with ion concentrations nearlyequal to those of human body fluid.

It is noted that the base material is preferably at least a basematerial with zirconia exposed on the surface, before the base materialsoaked in the simulated body fluid. The base material has preferably ahydrophilic group on the surface. Moreover, the hydrophilic group ispreferably bonded to a zirconium atom of zirconia in the base material.In this process, the bone-like apatite layer may be easily formed on thesurface in the simulated body fluid, according to the hydrophilic groupbonded to a zirconium atom of zirconia in the base material.

According to the hard tissue repairing material of this invention, ithas a hydrophilic group, which is bonded to a zirconium atom of zirconiain the base material. Thus the hard tissue repairing material has a highhardness, a high toughness, and good bioactive property that indicatesgood bonding to a living bone. Therefore, the hard tissue repairingmaterial can be used in bone repairing without a reinforcement e.g.,metal or plastics. It can be used in the femoral bone and the tibialbone, which is received with a large load. The hard tissue repairingmaterial can supersede a prosthetic titanium metal screw widely used asan artificial root of a tooth, because the hard tissue has sufficientmechanically property and high bioactive property. In this case of theartificial root of a tooth, the usage may not be limited in screw type.The hard tissue repairing material may not injure the living tissuebecause of ceramics. Therefore, the hard tissue repairing material ofzirconia ceramics of this invention is suitably used in a bone repairingmaterial and a implant e.g., an artificial root of a tooth.

BEST MODE FOR CARRYING OUT THE INVENTION

A hard tissue repairing material includes a base material containingzirconia. The base material has a hydrophilic group on the surface.Moreover, the hydrophilic group is bonded to a zirconium atom ofzirconia in the base material. The hydrophilic group has bioactiveproperty, so may easily induce a nucleus creation of apatite on thesurface of the base material in the living body or in the simulated bodyfluid. The tetragonal zirconia polycrystals is used because of highmechanical property. The base material may be composite incorporatingwith an alumina having good hardness. Therefore, the hard tissuerepairing material provides a high mechanical property and a highbioactive property.

In the first embodiment, several discs (diameter 11 mm, thickness 1 mm)of zirconia-alumina composite are prepared as the base materials. Thezirconia-alumina composite contains the tetragonal zirconia polycrystalswith 10 mol % ceria as against the zirconia as a stabilizing agent andthe alumina particles in 30 volume %. In the microstructure of thiscomposite materials, a basic structure has a mixed morphology of microand nano-composite materials, which have a submicron sized zirconiaparticles and alumina particles. Moreover, a part of the nanometer sizedalumina particles are trapped within the zirconia crystal particlesconsisting of matrix phase. The process of forming the hydrophilic groupon the surface of the base material is as following.

Several base materials are respectively soaked in 5 ml of concentratedhydrochloric acid, concentrated phosphoric acid, 50 volume % phosphoricacid, concentrated sulfuric acid, 50 volume % sulfuric acid, and 15mol/l sodium hydroxide solution holding at 95° C. for 4 days. Then thebase material are washed by distilled water, and dried up. This soakingprocess, in which the base materials are soaked in the acid solution orthe alkaline solution, is called the “chemical process” hereunder.

The base materials performed of the chemical process and the basematerials before the chemical process are soaked in the simulated bodyfluid (called “SBF” hereunder) (ion concentrations (mM): Na⁺ 142, K⁺5.0, Mg²⁺ 1.5, Ca²⁺ 2.5, Cl⁻ 148, HCO₃ ⁻ 4.2, HPO₄ ²⁻ 1.0, SO₄ ²⁻ 0.5)with 30 ml holding at pH 7.4, and 36.5° C. for several time. The surfaceof the base materials are analyzed by a thin film X-ray diffractionmethod (TF-XRD), X-ray photo-electron spectroscopy (XPS), before thechemical process, after the chemical process, and after soaking in SBF.Moreover, the surfaces are observed by scanning electron microscope(SEM). The element analysis is observed by Inductively coupled plasmaatomic emission spectrometry (ICPA). For the component contentsanalysis, the qualitative analysis is observed by Fourier transforminfrared spectroscopy (FT-IR), and the quantitative analysis is observedby thermal analysis. In the thermal analysis, a CO₂ gas and a H₂O gasare detected in a burning gas, so a carbonate ion (CO₃ ²⁻) content withrespect to the deposits is observed.

As a result of this analysis and observation, in TF-XRD patterns and SEMimages, the base materials preformed by the chemical process and notpreformed before soaking in the SBF have no difference. However, newspherical deposits are observed by SEM in the surface of the basematerials soaked in SBF for 14 days after the chemical processregardless of any solution of the chemical process. According to a peakof TF-XRD patterns of the base materials soaked in SBF belonging to anapatite, the deposits are identified to the apatite. The apatite, whichhas been soaked in 50 volume % phosphoric acid, has a Ca/P ration thatis 1.51 observed by ICPA, and has a carbonate ion content that is 2.64wt % with respect to the apatite observed by thermal analysis.Therefore, the apatite may be bone-like apatite. The amounts of thedeposits per area differ depending on the kind of solution of thechemical process. Thus the amounts of apatite are arranged in thefollowing order; 50 volume % phosphoric acid>50 volume % sulfuricacid>15 mol/l sodium hydroxide solution>concentrated hydrochloricacid>concentrated sulfuric acid>concentrated phosphoric acid. It isnoted that the apatite didn't have been deposited on the surface of thebase materials not performed by the chemical process.

The spectrum of 1 s orbital electron of oxide in XPS data is separatedinto Zr—OH, Al—OH, and adsorbed water (first group), ZrO₂, and Al₂O₃(second group). Then, in the case of the base materials performed in thechemical process, the spectrum strength of the Zr—OH group and the Al—OHgroup increase regardless of a kind of solution of the chemical process.Therefore, according to the chemical process, Zr—OH group and Al—OHgroup may be formed on the surface of the base materials. It isconsidered that the Zr—OH group induces the apatite nucleation, becausethe Al—OH cannot induce the apatite nucleation.

In the second embodiment, the base materials performed in the chemicalprocess in similar conditions of the first embodiment are prepared. Thebase materials performed in the chemical process are soaked in themolten salt, so that a calcium ion and a potassium ion are containedwithin the surface of the base materials. The steps of soaking in themolten salt are performed as following. A calcium carbonate and apotassium carbonate is mixed in a mixing ratio of 6:4, and this mixtureis melted at 850° C., then a carbonate molten salt is given. The basematerials, which have been preheated at 750° C., are soaked for onehour. Then the base materials are washed by distilled water, and dried.Hereunder, this process of soaking in the molten salt is called as the“molten salt process”. According to XPS analysis for the surface of thebase materials, peaks of a calcium and potassium is detected. Therefore,it is ascertained that the base materials have the calcium ion and thepotassium ion within the surface.

The base materials, which are performed in the chemical process and themolten salt process in this order, are soaked in the SBF with pH 7.4 and36.5° C. for 7 days. Many spherical bone-like apatite crystals form onthe surface of the base materials as observed by SEM.

In the third embodiment, the base materials performed in the chemicalprocess in similar conditions of the first embodiment are prepared. Thebase materials performed in the chemical process are soaked in themolten salt that is different from the second embodiment, so that acalcium ion and a sodium ion are contained within the surface of thebase materials. The steps of soaking in the molten salt are performed asfollowing. A calcium nitrate and a sodium nitrate is mixed in a mixingratio of 5:5, and this mixture is melted at 300° C., then a nitratemolten salt is given. The base materials, which have been preheated at200° C., are soaked for one hour. Then the base materials are washed bydistilled water, and dried. According to XPS analysis for the surface ofthe base materials, peaks of a calcium and sodium are detected.Therefore, it is ascertained that the base materials have the calciumion and the sodium ion within the surface.

The base materials, which are performed in the chemical process and themolten salt process in this order, are soaked in the SBF with pH 7.4 and36.5° C. for 7 days. Many spherical bone-like apatite crystals form onthe surface of the base materials as observed by SEM.

In the fourth embodiment, the base materials performed in the chemicalprocess in similar conditions of the first embodiment are prepared. Thebase materials performed in the chemical process are soaked in themolten salt that is different from the second and third embodiment, sothat a calcium ion and a sodium ion are contained within the surface ofthe base materials. The steps of soaking in the molten salt areperformed as following. A calcium chloride and a sodium chloride ismixed in a mixing ratio of 5:5, and this mixture is melted at 580° C.,then a chloride molten salt is given. The base materials, which havebeen preheated at 480° C., are soaked for one hour. Then the basematerials are washed by distilled water, and dried. According to XPSanalysis for the surface of the base materials, peaks of a calcium andsodium is detected. Therefore, it is ascertained that the base materialshave the calcium ion and the sodium ion within the surface.

The base materials, which are performed in the chemical process and themolten salt process in this order, are soaked in the SBF with pH 7.4 and36.5° C. for 7 days. Many spherical bone-like apatite crystals form onthe surface of the base materials as observed by SEM.

In the fifth embodiment, the base materials (disc with diameter 11 mm,thickness 1 mm) of zirconia-alumina composite are prepared. The basematerials are soaked in the molten salt, so that a calcium ion and apotassium ion are contained within the surface of the base materials.The steps of soaking in the molten salt are performed as following. Acalcium carbonate and a potassium carbonate is mixed in a mixing ratioof 6:4, and this mixture is melted at 850° C., then a carbonate moltensalt is given. The base materials, which have been preheated at 750° C.,are soaked for one hour. Then the base materials are washed by distilledwater, and dried. According to XPS analysis for the surface of the basematerials, peaks of a calcium and potassium is detected. Therefore, itis ascertained that the base materials have the calcium ion and thepotassium ion within the surface.

Several base materials are respectively soaked in 5 ml of 50 volume %phosphoric acid, and 15 mol/l sodium hydroxide solution holding at 95°C. for 4 days. Then the base material are washed by distilled water, anddried up.

The base materials, which are performed in the molten salt process andthe chemical process in this order, are soaked in the SBF with pH 7.4and 36.5° C. for 7 days. Many spherical bone-like apatite crystals formon the surface of the base materials as observed by SEM. The bone-likeapatite has a Ca/P ratio that is within 1.48 to 1.56, and has acarbonate ion content that is within 2.5 to 3.5 wt % with respect to thebone-like apatite. It is noted that the bone-like apatites are similarlyobserved on the base materials, which is performed in the molten saltprocess of the third and the fourth embodiment and the chemical processin this order.

1-13. (canceled)
 14. A hard tissue repairing material, comprising: abase material made of zirconia including a plurality of zirconium atoms;and hydrophilic groups each bonded to one of the zirconium atomsconstituting the surface of the base material, wherein the hydrophilicgroups exist on the surface of the base material.
 15. A hard tissuerepairing material according to claim 14, wherein said zirconia in thebase material is a tetragonal zirconia polycrystal.
 16. A hard tissuerepairing material according to claim 14, wherein said base materialincludes at least a ceria as a stabilizing agent.
 17. A hard tissuerepairing material according to claim 14, wherein said hydrophilicgroups are hydroxyl groups.
 18. A hard tissue repairing materialaccording to claim 14, wherein said base material contains at least anionic component that is selected from the group consisting of calciumion, sodium ion, potassium ion, and phosphate ions within said surface.